Coil-helix and sheet-helix block copolymers via macroinitiation from telechelic ROMP polymers

Abstract

Coil-helix and sheet-helix block copolymers are synthesized by combining the ring-opening metathesis polymerization (ROMP) of norbornene or paracyclophanediene with the anionic polymerization of phenyl isocyanide. Key to the design is the use of an μ-ethynyl palladium (II) functionalized chain-transfer agent (CTA) that can be exploited in a stepwise manner for the termination of ROMP and the initiation of the anionic polymerization. Both the coil- and sheet-macroinitiators, and the ensuing covalent block copolymers, are analyzed using 1H NMR spectroscopy and gel-permeation chromatography. In all cases, the Pd-end group is maintained and all polymers demonstrate a monomodal distribution with dispersities (Đ) of 1.1–1.4. The resulting helix-coil and helix-sheet block copolymers formed by the macroinitiation route still demonstrate their intrinsic properties (fluorescence, preferential helix-sense). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2991–2998.